JP5654443B2 - Carbodiimide compound and base oil / water repellency imparting composition - Google Patents

Description

  The present invention relates to a carbodiimide compound or a mixture of carbodiimide compounds. The invention further relates to a composition comprising said carbodiimide compound or mixture of carbodiimide compounds and a fluorinated compound. The present invention also relates to a method for imparting oil and water repellency properties to a substrate.

  In particular, a composition for making a base material such as a fibrous base material such as a fabric oil- and water-repellent has been known for a long time in the technical field. Fluorochemical compounds are well known to be very effective especially for imparting oil and water repellency to substrates such as fabric substrates. For example, the fluorochemical composition can be based on a fluorochemical acrylate or methacrylate derived from the polymerization of an acrylate or methacrylate monomer having a fluorinated group and optionally one or more non-fluorinated monomers. Such compositions are described, for example, in US Pat. No. 3,660,360, US Pat. No. 5,876,617, US Pat. No. 4,742,140, US Pat. No. 6,121. 372, US Pat. No. 6,126,849 and EP 1 329 548.

  Additives have been used to assist the oil and water repellency of fluorochemical treatment agents. U.S. Pat. No. 4,215,405 provides a fabric with water and oil repellency that is resistant to washing and dry cleaning by applying a blend of fluoroaliphatic vinyl polymer and carbodiimide. Teach that.

  Fluorochemicals are generally expensive. Accordingly, hydrocarbon additives, also called extenders, have been developed to reduce costs. Modified synthetic resins, waxes, melamine resins, paraffin emulsions and similar products have been used as bulking agents.

  US Pat. No. 5,132,028 discloses a composition that imparts water repellency and oil repellency to a fabric such as silk. This composition is a fluorochemical type; Carbodiimide; and; at least one component selected from the group consisting of plasticizers, metal alcoholates or esters, zirconium salts, alkyl ketene dimers, aziridines, and alkenyl succinic anhydrides.

  EP 0 713 863 discloses a carbodiimide compound obtainable from a reaction mixture comprising an isocyanate compound and a monofunctional alcohol in a non-reactive solvent in the presence of a suitable catalyst. And the monofunctional alcohol is characterized in that it contains no isocyanate-reactive hydrogen atoms except for hydroxy groups, and the monofunctional alcohol is a branched aliphatic alcohol containing at least 8 carbon atoms, and a fluorochemical It is characterized by a composition comprising an oil / water repellent and the carbodiimide compound.

  Aqueous fluorochemical compositions are generally preferred from an environmental standpoint. In many commercially available aqueous fluorochemical compositions, the fluorochemical compound is dispersed in water with the aid of a surfactant. Such compositions have been found to present problems in certain application methods. In particular, in applications where the fluorochemical composition is applied by contacting the substrate with the composition in a bath and then guiding the substrate through a set of rolls, the composition was applied to the substrate several times. Later, the roll may be deposited. This is undesirable because it requires application to be interrupted and the roll cleaned, leading to increased production costs for the treated substrate. This behavior is further influenced by the nature of the fluorochemical composition and the nature of the substrate being processed, with some substrates and fluorochemical compositions causing this problem earlier than others. Increasing the amount of surfactant in the composition can alleviate the problem. However, increasing surfactant levels have been found to adversely affect the water repellent (oil) performance of the composition.

  Accordingly, it would be desirable to reduce or even eliminate the aforementioned problems. The solution to the problem will preferably be environmentally friendly and economical. Preferably, the oil and / or water repellency properties that can be achieved on the substrate with the composition should not be adversely affected when reducing or eliminating roll deposit problems. It would be further desirable to find new extenders, particularly extenders that can improve the effect of fluorination in aqueous systems. It would be further desirable to provide a composition and process that imparts both static and particularly dynamic water repellency to a fibrous substrate without the aforementioned problems associated with roll deposits.

  In one aspect, the present invention is derived from a carbodiimidization reaction of at least one oligomer having at least one isocyanate group and comprising at least two repeating units derived from one or more ethylenically unsaturated monomers. A carbodiimide compound or a mixture of carbodiimide compounds.

  In a further aspect, the present invention relates to a method of forming the aforementioned carbodiimide compound or mixture of carbodiimide compounds.

（式中、Ｇ³およびＧ⁴は各々独立して末端基を表し、Ｍ_hは１つ以上のエチレン性不飽和モノマーから誘導される２つ以上の繰返し単位を表し、Ｌ²は有機二価結合基を表し、Ｑ³はカテナリまたは非カテナリヘテロ原子を１つ以上含有し得る炭化水素基またはカテナリまたは非カテナリヘテロ原子を１つ以上含有し得る部分または完全フッ素化炭化水素基を表し、Ａ³およびＡ⁴は各々独立して有機ジ−またはトリイソシアネート化合物からイソシアネート基を除去することにより得られるそれらの残渣を表し、Ｘ³およびＸ⁴は各々独立してＯ、ＳまたはＮＨを表し、ｓは１〜２０の値を有しおよびｔは１または２であり、Ｌ³は有機三価結合基を表しおよびＬ⁴はカテナリまたは非カテナリヘテロ原子を１つ以上任意に含有し得る炭化水素基、またはカテナリまたは非カテナリヘテロ原子を１つ以上含有し得る部分または完全フッ素化炭化水素基を表し、ここで、Ｑ¹およびＱ²のいずれか一方が式（Ａ）、（Ｂ）、（Ｄ）または（Ｅ）の基に対応する）
から選択される） In yet a further aspect, the present invention relates to a carbodiimide compound or mixture, wherein one or more of the carbodiimide compounds can be represented by formula (I).
^{Q 1 -X 1 -CONH- (A 1} - (N = C = N) q) m -A 2 -NHCOX 2 -Q 2 (I)
Wherein X ¹ and X ² each independently represent O, S or NH, and A ¹ and A ² each independently represent those obtained by removing isocyanate groups from organic di- or triisocyanate compounds. Wherein q is 1 or 2, m has a value of 1-20, and Q ¹ and Q ² are hydrocarbon groups, catenary or a group that may contain one or more catenary or non-catenary heteroatoms A moiety that may contain one or more non-catenary heteroatoms or a fully fluorinated hydrocarbon group and a functional group corresponding to any of the following formulas:

Wherein G ³ and G ⁴ each independently represent a terminal group, M _h represents two or more repeating units derived from one or more ethylenically unsaturated monomers, and L ² represents an organic divalent group. Q ³ represents a linking group, Q ³ represents a hydrocarbon group that can contain one or more catenary or non-catenary heteroatoms, or a partial or fully fluorinated hydrocarbon group that can contain one or more catenary or non-catenary heteroatoms; ³ and A ⁴ each independently represent those residues obtained by removing isocyanate groups from an organic di- or triisocyanate compound, X ³ and X ⁴ each independently represent O, S or NH; s has a value of 1 to 20 and t is 1 or 2, L ³ represents an organic trivalent linking group, and L ⁴ is a hydrocarbon optionally containing one or more catenary or non-catenary heteroatoms Base , Or a moiety or a fully fluorinated hydrocarbon group that may contain one or more catenary or non-catenary heteroatoms, wherein either Q ¹ or Q ² is of the formula (A), (B), (D ) Or (E)
Selected from)

  In yet a further aspect, the present invention relates to a fluorinated compound and at least one oligomeric carbodiimide having at least one isocyanate group and comprising at least two repeating units derived from one or more ethylenically unsaturated monomers. The present invention relates to a composition comprising a carbodiimide compound or a mixture of carbodiimide compounds, which is derived from a conversion reaction.

  In a still further aspect, the present invention relates to a method of treating a substrate with the aforementioned composition for imparting water repellency and / or oil repellency to a substrate, particularly a fibrous substrate. In particular, it has been found that the composition is suitable for use in application methods in which the substrate is directed to pass through a roll.

  The carbodiimide compound or mixture of carbodiimide compounds of the present invention can act as an excellent bulking agent in the treatment of substrates, thus allowing more effective use of typically more expensive fluorinated compounds. Was found. Compositions comprising a carbodiimide compound or mixture of carbodiimide compounds and a fluorinated compound generally provide the substrate with effective static and / or dynamic water repellency.

  According to certain embodiments, a carbodiimide compound or mixture of carbodiimide compounds of the present invention can be prepared in a three-step reaction, but generally it will not be necessary to separate the reaction products after a separate step. . That is, the reaction can be carried out in three steps in a single reactor. In the first step, a functionalized oligomer having at least two repeating units is prepared, which is reacted in the second step to form an oligomer having at least one isocyanate group. In the third step, the oligomer is further reacted to form carbodiimide. The term “functionalized oligomer” means that an oligomer containing a functional group capable of reacting with an isocyanate is prepared.

In the first step, a functionalized oligomer having at least two repeating units is prepared by free radical oligomerization of one or more ethylenically unsaturated monomers, typically non-fluorinated ethylenically unsaturated monomers. Can Examples of the ethylenically unsaturated monomer include those represented by the general formula (II).
R _h −C (R) = CR ₂ (II)
Where R _h represents H, Cl, or a hydrocarbon group that may contain one or more catenary (ie, only bonded to carbon in the chain) or non-catenary heteroatoms, where R is each The same or different and represents H, lower alkyl having 1 to 4 carbon atoms, Cl or Br.

  The term “hydrocarbon group” in the context of the present invention means either hydrogen and carbon, and optionally any organic moiety that is substantially free of fluorine containing one or more substituents.

Suitable ethylenically unsaturated monomers are known and are generally commercially available. Examples of such compounds include, for example, allyl esters such as allyl acetate and allyl heptanoate; alkyl vinyl ethers or alkyl allyl ethers such as cetyl vinyl ether, dodecyl vinyl ether, 2-chloroethyl vinyl ether, ethyl vinyl ether; acrylic acid, methacrylic acid, Acids, α-chloroacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and their anhydrides and esters (vinyl, allyl, methyl, butyl, isobutyl, hexyl, heptyl, 2- Unsaturated acids such as ethyl-hexyl-, cyclohexyl-, lauryl-, stearyl-, isobornyl-, octadecyl-, hexadecyl- or alkoxyethyl acrylate and methacrylate); acrylonite , Methacrylonitrile, 2-chloroacrylonitrile, 2-cyanoethyl acrylate, alkyl cyanoacrylate and other α-β unsaturated nitriles; allyl alcohol, allyl glycolic acid, acrylamide, methacrylamide, n-diisopropylacrylamide, diacetacrylamide, N Α, β-unsaturated carboxylic acid derivatives such as N, diethylaminoethyl methacrylate, Nt-butylaminoethyl methacrylate; styrene and derivatives thereof such as vinyltoluene, α-methylstyrene, α-cyanomethylstyrene; , Halogenated propylene, halogenated isobutene, halogenated 3-chloro-1-isobutene, halogenated isoprene, and allyl halide or vinyl halide (vinyl chloride and chloride) And a general class of radically polymerizable ethylene compounds such as lower olefin hydrocarbons containing halogen such as vinylidene. Other useful monomers include monomers containing urethane groups, such as the reaction product of 2-hydroxy-ethyl (meth) acrylate and a monofunctional isocyanate such as octadecyl isocyanate. Specific suitable monomers include octadecyl (meth) acrylate, hexadecyl (meth) acrylate, methyl methacrylate, butyl (meth) acrylate, isobutyl (meth) acrylate and isobornyl (meth) acrylate, ethylhexyl methacrylate, urethane groups ( Those selected from the group consisting of ( meth) acrylates and mixtures thereof.

  Free radical oligomerization is typically carried out in the presence of mono- or bifunctional hydroxy- or amino-functionalized chain transfer agents to prepare mono- or bifunctional oligomers, respectively. Examples of monofunctional chain transfer agents selected from 2-mercaptoethanol, 3-mercapto-2-butanol, 3-mercapto-2-propanol, 3-mercapto-1-propanol and 2-mercapto-ethylamine Is mentioned. A particularly suitable monofunctional chain transfer agent is 2-mercaptoethanol. Examples of bifunctional chain transfer agents include those having two hydroxyl or amino groups, or hydroxy and amino groups. A particularly suitable example of a bifunctional chain transfer agent is 3-mercapto-1,2-propanediol.

  The functionalized oligomer should generally contain a sufficient number of repeating units to provide the oligomer moiety. The oligomer suitably comprises 2 to 40, especially 2 to 20 repeating units derived from one or more ethylenically unsaturated monomers. According to certain embodiments, the oligomer has 3 to 15 repeat units. According to another embodiment, the oligomer has 4-15 repeat units.

To prepare the functionalized oligomer, a radical initiator can be used to initiate the oligomerization. Radical initiators include those known in the art, and in particular azo such as 2,2′-azobisisobutyronitrile (AIBN) and 2,2′-azobis (2-cyanopentane). Compounds, hydroperoxides such as cumene, t-butyl, and t-amyl hydroperoxide, peroxyacid esters such as t-butylperbenzoate and di-t-butylperoxyphthalate, diacyl such as benzoyl peroxide and lauroyl peroxide Peroxides are mentioned .

  The oligomerization reaction can be carried out in any solvent suitable for organic radical reactions. Particularly suitable solvents are those that do not interfere with the isocyanate reaction that forms the carbodiimide in the second and third steps. The reactants can be present in the solvent at any suitable concentration, for example from about 5 percent to about 90 percent by weight based on the total weight of the reaction mixture. Examples of suitable solvents include aliphatic and alicyclic hydrocarbons (eg, hexane, heptane, cyclohexane), ethers (eg, diethyl ether, glyme, diglyme, diisopropyl ether), esters (eg, ethyl acetate, butyl acetate) ), Ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone) and mixtures thereof.

  The oligomerization reaction can be performed at any temperature suitable for performing a free radical oligomerization reaction. The specific temperature and solvent used can be easily selected by those skilled in the art by considering the solubility of the reagent, the temperature required for the use of the specific initiator, the desired molecular weight, and the like. Although it is not practical to list specific temperatures suitable for all initiators and all solvents, generally suitable temperatures are from about 30 ° C to about 150 ° C.

In the second step, an oligomer having at least one isocyanate group is prepared by a condensation reaction between a functionalized oligomer and an excess of polyisocyanate, ie di- or triisocyanate. In general, the second reaction step is also carried out in the presence of one or more further isocyanate-reactive compounds. Such further isocyanate-reactive compounds are compounds that typically contain one or two isocyanate-reactive groups and include mono- and difunctional alcohols, thiols and amines. The further isocyanate-reactive compounds are generally non-fluorinated but can also be partially or fully fluorinated. A single compound or a mixture of different compounds may be used. Examples include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, n-amyl alcohol, t-amyl alcohol, 2-ethylhexanol, glycidol, (iso) stearyl. Branched long chain alkanols such as alcohols, alkanols such as behenyl alcohol, gerber alcohols (2-alkyl alkanols with C-14 to C-24 alkyl chains, available from Henkel), such as polyethylene glycol methyl or ethyl ether, Hydroxyl-terminated methyl or ethyl ethers of random or block copolymers of polysiloxane groups containing ethylene oxide and / or propylene oxide and alcohol They include alcohols containing poly (oxyalkylene) groups such as ether. Further examples include diols such as 1,4-butanediol, 1,6-hexanediol, 1-10-decanediol, 4,4′-isopropylidenediphenol (bisphenol A); polycaprolactone diol, fatty acid dimer diol And an oxyalkylene group having 2 to 4 carbon atoms (——OCH ₂ CH ₂ ——, —O (CH ₂ ) ₄ ——, —OCH ₂ CH ₂ CH ₂ ——, —OCH ( CH ₃ ) CH ₂ --- and --OCH (CH ₃ ) CH (CH ₃ )-(polypropylene glycol, the oxyalkylene units in the poly (oxyalkylene) are the same or exist as a mixture A polyester diol such as a poly (oxy) alkylene diol with glycerol monos And ester diols such as terate and polysiloxane group-containing diols.

  Further suitable isocyanate-reactive compounds include amino-terminated polyethylene oxide or propylene oxide or copolymers thereof, amino-terminated methyl or ethyl ethers of polyethylene oxide or polypropylene oxide, or copolymers thereof, and amino groups such as amino-terminated polysiloxanes. Containing compounds. Fluorinated isocyanate-reactive compounds that can be used include, for example, partially fluorinated or perfluorinated polyethers having one or two isocyanate-reactive groups such as hydroxyl, amino and thiol groups. Still further, fluorinated isocyanate-reactive compounds that can be used are partial or fully fluorinated aliphatic compounds having one or two isocyanate-reactive groups such as hydroxyl groups, amino groups and thiol groups. Examples of the latter include perfluorinated aliphatic mono-alcohols having up to 3, 4 or 14 carbon atoms.

  Further, examples of the more preferable isocyanate-reactive compound include thiol group-containing compounds such as 1,4-butanedithiol and 1,6-hexanedithiol.

  Particularly suitable further isocyanate-reactive compounds include monofunctional alcohols such as (iso) stearyl alcohol and C-18 2-alkylalkanols; ester diols such as glycerol monostearate, amino- or hydroxy group-containing polysiloxanes and these Of the mixture.

  The isocyanate-reactive compounds can be used alone or in combination. The isocyanate-reactive compound can be present at about 50 mole percent or less based on the total amount of isocyanate functional groups.

  Polyisocyanates for use according to the present invention include aliphatic and aromatic di- and triisocyanates. Examples of diisocyanates include 4,4′-methylene diphenylene diisocyanate (MDI), 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, o, m, and p-xylylene diisocyanate, 4,4′-diisocyanate. Isocyanatodiphenyl ether, 3,3′-dichloro-4,4′-diisocyanatodiphenylmethane, 4,4′-diphenyl diisocyanate, 4,4′-diisocyanatodibenzyl, 3,3′-dimethoxy-4,4 '-Diisocyanatodiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenyl, 2,2'-dichloro-5,5'-dimethoxy-4,4'-diisocyanatodiphenyl, 1, 3-diisocyanatobenzene, 1,2-naphthylene diisocyanate, 4-chloro-1,2-naphth Diisocyanate, 1,3-naphthylene diisocyanate, and 1,8-dinitro-2,7-naphthylene diisocyanate; alicyclic diisocyanates such as 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate; 3- Isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate; aliphatic diisocyanates such as 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, and 1,2-ethylene diisocyanate Cyclic diisocyanates such as isophorone diisocyanate (IPDI) and dicyclohexylmethane-4,4′-diisocyanate. Examples of triisocyanates include aliphatic triisocyanates such as 1,3,6-hexamethylene triisocyanate, and polymethylene polyphenyl isocyanate (PAPI, Voranate®), DESMODUR (registered) Aromatic triisocyanates such as TM R (tri- (4-isocyanatophenyl) -methane, available from Bayer) and DESMODUR® L (available from Bayer) Is mentioned. Also useful are biuret-containing triisocyanates (such as those available from Bayer as DESMODUR® N-100) and isocyanurate-containing triisocyanates (Huls AG, Germany). Isocyanates containing internal isocyanate-derived moieties such as those available from Germany as IPDI-1890 and those available from Bayer such as Desmodur N-3300.

  Particularly suitable polyisocyanates include aromatic polyisocyanates such as MDI and 2,4-toluene diisocyanate and hexamethylene diisocyanate, Desmodur® N, Desmodur® W and Desmodur. Aliphatic polyisocyanates such as Desmodur® N-3300.

  Oligomers having at least one isocyanate group can be prepared by condensation reactions carried out under conventional conditions well known to those skilled in the art. The condensation reaction is preferably carried out in a polar solvent such as ethyl acetate, acetone, methyl isobutyl ketone, etc. under dry conditions. Suitable reaction temperatures will be readily determined by those skilled in the art based on the particular reagents, solvents, and catalysts used. Although it is not practical to enumerate specific temperatures suitable for all situations, generally suitable temperatures are between about room temperature and about 120 ° C.

In certain embodiments of the invention, the oligomer having at least one isocyanate group may be represented by formula (III).
_{^{G 1 -M h -G 2 (III}} )
Where M _h represents two or more repeating units derived from one or more ethylenically unsaturated monomers, and G ¹ and G ² each independently represent a terminal group, wherein at least one terminal The group contains an isocyanate group. In one embodiment of the invention, one of the end groups does not contain an isocyanate group and the other group contains one or two isocyanate groups. In certain embodiments, one of the end groups is free of isocyanate groups, and other groups of the formula ^{-L 1 -CO-NH-Z-} NCO
Wherein L ¹ represents O or NH, and Z represents an aliphatic or aromatic group.

  In the third step, a carbodiimide compound or a mixture of carbodiimide compounds is prepared according to, for example, Kew Wagner et al., Angew. Chem. Int. Ed. Engl. 20: 819-830 (1981); R. By Sandler et al., Org. Functional Group Prep. 2, pp. 205-222 (1971) and A Williams et al., Chem. Rev. 81, 589-636 (1981), and can be formed by the condensation reaction of oligomers having at least one isocyanate group in the presence of a suitable catalyst. The preparation of urethane-containing or urethane-terminated polycarbodiimides is described, for example, in US Pat. No. 2,941,983 and T.W. W. J. Campbell et al. Org. Chem. 28, 2069 (1963). Representative examples of suitable catalysts are described, for example, in US Pat. No. 2,941,988, US Pat. No. 3,862,989 and US Pat. No. 3,896,251. Yes. Examples include 1-ethyl-3-phospholine, 1-ethyl-3-methyl-3-phosphorin-1-oxide, 1-ethyl-3-methyl-3-phosphorin-1-sulfide, 1-ethyl-3- Methyl-phosphoridine, 1-ethyl-3-methyl-phosphoridine-1-oxide, 3-methyl-1-phenyl-3-phosphorin-1-oxide and bicyclic terpene alkyl or hydrocarbyl aryl phosphine oxide or camphene phenylphosphine oxide. Can be mentioned.

  The particular amount of catalyst used will depend largely on the reactivity of the catalyst itself and the organic polyisocyanate used. A catalyst concentration range of 0.05 to 5 parts per 100 parts of oligomer having at least one isocyanate group is generally suitable. The carbodiimidization reaction can include additional isocyanate compounds other than the isocyanate-containing oligomer. Such further isocyanate compounds include mono-isocyanates as well as polyisocyanates such as those described above.

式中、Ｇ³およびＧ⁴は各々独立して末端基を表し、Ｍ_hは１つ以上のエチレン性不飽和モノマーから誘導される２つ以上の繰返し単位を表し、Ｌ²は有機二価結合基を表し、Ｑ³はカテナリまたは非カテナリヘテロ原子を１つ以上含有し得る炭化水素基またはカテナリまたは非カテナリヘテロ原子を１つ以上含有し得る部分または完全フッ素化炭化水素基を表し、Ａ³およびＡ⁴は各々独立して有機ジ−またはトリイソシアネート化合物からイソシアネート基を除去することにより得られるそれらの残渣を表し、Ｘ³およびＸ⁴は各々独立してＯ、ＳまたはＮＨを表し、ｓは１〜２０の値を有しおよびｔは１または２であり、Ｌ³は有機三価結合基を表しおよびＬ⁴はカテナリまたは非カテナリヘテロ原子を１つ以上任意に含有し得る炭化水素基またはカテナリまたは非カテナリヘテロ原子を１つ以上含有し得る部分または完全フッ素化炭化水素基を表し；ここで、Ｑ¹およびＱ²のいずれか一方が式（Ａ）、（Ｂ）、（Ｄ）または（Ｅ）の基に対応する。 In certain embodiments according to the present invention, the carbodiimide compound can be represented by formula (I).
^{Q 1 -X 1 -CONH- (A 1} - (N = C = N) q) m -A 2 -NHCOX 2 -Q 2 (I)
In which X ¹ and X ² each independently represent O, S or NH, and A ¹ and A ² each independently represent those obtained by removing isocyanate groups from organic di- or triisocyanate compounds. Represents a residue, q is 1 or 2, m has a value of 1-20, and Q ¹ and Q ² are hydrocarbon groups, catenary or non-catalysts which may contain one or more catenary or non-catenary heteroatoms It is selected from a moiety that may contain one or more catenary heteroatoms or a fully fluorinated hydrocarbon group and a functional group corresponding to any of the following formulas.

Wherein G ³ and G ⁴ each independently represent a terminal group, M _h represents two or more repeating units derived from one or more ethylenically unsaturated monomers, and L ² represents an organic divalent bond. Q ³ represents a hydrocarbon group that can contain one or more catenary or non-catenary heteroatoms, or a partial or fully fluorinated hydrocarbon group that can contain one or more catenary or non-catenary heteroatoms, and A ³ And A ⁴ each independently represent those residues obtained by removing isocyanate groups from organic di- or triisocyanate compounds, X ³ and X ⁴ each independently represent O, S or NH, and s Has a value of 1 to 20 and t is 1 or 2, L ³ represents an organic trivalent linking group, and L ⁴ is a hydrocarbon group optionally containing one or more catenary or non-catenary heteroatoms Ma Or a moiety or a fully fluorinated hydrocarbon group that may contain one or more catenary or non-catenary heteroatoms; wherein either Q ¹ or Q ² is represented by the formula (A), (B), (D ) Or (E).

The groups A ¹ , A ² , A ³ and A ⁴ (hereinafter collectively referred to as “A-groups”) each independently remove the isocyanate group from the organic di- or triisocyanate compound. Represents those residues obtained by The A-groups may be the same or different. When A is trivalent derived from triisocyanate, branched or crosslinked polycarbodiimides can be obtained. Different A-groups can be used together to slightly branch and modify properties. Substituents can be present in A as long as they do not contain isocyanate-reactive hydrogen atoms. Particularly preferred groups A are unsubstituted organic linking groups such as, for example:

The end groups G ³ and G ⁴ typically represent hydrogen or the residue of the initiator used to prepare the functionalized oligomer.

The linking groups L ² and L ³ each represent an organic divalent or trivalent linking group. Examples thereof include divalent or trivalent aliphatics including straight chain branched or cyclic aliphatic groups or aromatic groups. The linking groups L ² and L ³ generally contain 1 to 30 carbon atoms, for example 2 to 12 carbon atoms.

The terminal group Q ³ represents an optionally partially or fully fluorinated hydrocarbon group that may contain one or more catenary or non-catenary heteroatoms. Q ³ generally has 1 to 50 carbon atoms. The terminal group Q ³ can represent, for example, a residue of a monofunctional isocyanate-reactive compound, for example a residue of the above-mentioned isocyanate-reactive compound obtained by removal of an isocyanate-reactive group. Examples of Q ³ are include monovalent aliphatic linear branched or cyclic aliphatic group or an aromatic group include partially or fully fluorinated aliphatic group or partially or fully fluorinated polyether groups. Particular useful examples for the end group Q ³ include linear or branched aliphatic end sites having at least 8 carbon atoms.

The linking group L ⁴ represents an aromatic or aliphatic hydrocarbon group that can optionally contain one or more catenary or non-catenary heteroatoms. The linking group L ⁴ can represent, for example, a residue of a bifunctional isocyanate-reactive compound obtained after removal of an isocyanate-reactive group from a difunctional isocyanate-reactive compound as described above. Examples include divalent aliphatic groups, including straight chain branched or cyclic aliphatic groups or aromatic groups, as well as partially or fully fluorinated aliphatic groups. Aliphatic groups can contain one or more catenary or non-catenary heteroatoms such as oxygen and nitrogen. Specific preferred examples of L ⁴ include the following formulas:

  The preparation of carbodiimide results in a mixture of compounds, and therefore the general formula (III) should be understood as representing a mixture of compounds, so the indices q, m, t and s in formula (III) are It will be further understood by those skilled in the art to represent the molar amount of the relevant units in such a mixture.

  After completion of the carbodiimidization reaction, the final reaction mixture can be dispersed in water using a surfactant or mixture of surfactants in an amount sufficient to stabilize the dispersion. A typical dispersion will contain water in an amount of about 70-20000 parts by weight based on 100 parts by weight of the carbodiimide compound or mixture of carbodiimide compounds. The surfactant or mixture of surfactants is preferably present in an amount of about 1 to 25 parts by weight, preferably about 5 to 15 parts by weight, based on 100 parts by weight of the carbodiimide compound or mixture of carbodiimide compounds. Conventional cationic, nonionic, anionic and zwitterionic surfactants and mixtures of nonionic and charged surfactants are preferred.

  Commercially available surfactants that can be used include Arquad (R) T-50 from Akzo-Nobel, Arquad (R) MCB-50, Etquad (Ethoquad). ) (R) C-12 and Etoquad (R) 18-25; and Tergitol (R) TMN-6 and Tergitol available from Rohm & Haas ) (Registered trademark) 15S30.

Fluorinated compounds suitable for use in the compositions according to the present invention include any of the fluorochemical group-containing organic compounds, including polymers and oligomeric compounds, known in the art to impart water and oil repellency to the substrate. Can be mentioned. These polymeric and oligomeric fluorinated compounds are typically fluorochemicals containing perfluorinated carbon chains having from 3 to about 20 carbon atoms, typically from about 4 to about 14 carbon atoms. Contains one or more groups. These fluorochemical groups can contain straight chain, branched chain, or cyclic fluorinated alkylene groups or any combination thereof. The fluorochemical group preferably does not include polymerizable olefinic unsaturation and can optionally contain catenary heteroatoms such as oxygen, divalent or hexavalent sulfur, or nitrogen. Although fully fluorinated groups are preferred, hydrogen or chlorine atoms can also be present as substituents as long as there is no more than one atom for every two carbon atoms. It is further preferred that any of the fluorochemical groups contain from about 40% to about 80% fluorine by weight, more preferably from about 50% to about 78% fluorine by weight. The terminal portion of the group is generally fully fluorinated and preferably contains at least 7 fluorine atoms. Perfluorinated aliphatic groups (ie of the formula C _n F _{2n + 1} —) are the most preferred fluorochemical groups.

  Representative examples of suitable fluorinated compounds include fluorochemical urethanes, ureas, esters, ethers, alcohols, epoxides, allophanates, amides, amines (and their salts), acids (and their salts), carbodiimides, guanidines, oxazolidinones. , Isocyanurates, biurets, acrylates and methacrylates homopolymers and copolymers, and mixtures thereof.

In one particular embodiment, the fluorinated compound comprises a fluorinated polymer comprising one or more repeating units derived from a fluorinated monomer corresponding to formula (IV).
R _f −L ⁵ −C (R) = CR ₂ (IV)
In which R _f represents a fluorinated aliphatic group or a perfluorinated polyether group, L ⁵ represents an organic divalent linking group, and R each independently have hydrogen or 1 to 3 carbon atoms. Represents a lower alkyl group.

The fluorinated aliphatic group R _f in the fluorinated monomer is typically a perfluorinated aliphatic group. This can be linear, branched, or cyclic or a combination thereof. The R _f radical has at least 3 to 18 carbon atoms, preferably 3 to 14, in particular 4 to 10 carbon atoms, and preferably about 40% to about 80% fluorine by weight, more preferably Contains about 50% to about 79% fluorine by weight. The terminal portion of the R _f radical is a perfluorinated site and preferably contains at least 7 fluorine atoms (eg, CF ₃ CF ₂ CF ₂ —, (CF ₃ ) ₂ CF—, F ₅ SCF ₂ —). Will. Preferred R _f radicals are those of the perfluorinated aliphatic radical of the formula C _n F _{2n + 1} —, where n is 3-18, in particular 4-10. A compound in which the R _f radical is C ₄ F ₉ — is generally more environmentally acceptable than a compound in which the R _f radical consists of a perfluorinated group having more carbon atoms.

The R _f group can also be a perfluorinated polyether group. Perfluorinated polyether groups R _f can include saturated or unsaturated and linear, branched, and / or cyclic structures that can be substituted with one or more oxygen atoms. Preferably it is a perfluorinated group (ie, all C—H bonds are replaced by C—F bonds). _{- (C n F 2n) -} , - (C n F 2n O) -, - (CF (Z)) -, - (CF (Z) O) -, - (CF (Z) C n F 2n O) _{-, - (C n F 2n} CF (Z) O) -, - (CF 2 CF (Z) O) -, and it is more preferable to include perfluorinated repeating units selected from the group of combinations thereof . In these repeating units, Z is a perfluoroalkyl group, an oxygen-substituted perfluoroalkyl group, a perfluoroalkoxy group, or an oxygen-substituted perfluoroalkoxy group (all of which are linear, branched, or cyclic). And preferably have from about 1 to about 9 carbon atoms and from 0 to about 4 oxygen atoms). End _{groups, (C n F 2n + 1} ) - can be a - or _{(C n F 2n + 1 O} ). In these repeating units or terminal groups, n is 1 or more, and preferably from about 1 to about 4. Particularly preferred approximate average structures for perfluoropolyether groups include C ₃ F ₇ O (CF (CF ₃ ) CF ₂ O) _p CF (CF ₃ ) — and CF ₃ O (C ₂ F ₄ O) _p CF _{2— and} the average value of p is from 1 to about 50. As synthesized, these compounds typically include a mixture of polymers. The approximate average structure is the approximate average of a mixture of polymers.

The organic divalent linking group L ⁵ in the above formula (IV) links a perfluorinated aliphatic group or perfluorinated polyether group R _f to a free radical polymerizable group, and this is generally a non-fluorinated organic bond It is a group. The linking group can be a chemical bond, but preferably contains from 1 to about 20 carbon atoms, and can optionally contain oxygen, nitrogen, or sulfur-containing groups or combinations thereof. The linking group is preferably free of functional groups that substantially interfere with free radical oligomerization (eg, polymerizable olefin double bonds, thiols, and other such functional groups known to those skilled in the art). . Examples of suitable organic divalent linking groups include
^* —COQ′—R ¹ —Q ″ —CO—, ^* —COO—CH ₂ —CH (OH) —R ¹ —Q′—CO—, ^* —L′—Q′—CONH—L ″ — ^{, * -R 1 -Q'-CO- *} -COQ'-R 1 -, - R 1 -, * -COQ'-R 1 -Q'-, * -SO 2 NR a -R 1 -Q'- _{^{, * -SO 2 NR a -R 1}} - and _{^{* -SO 2 NR a -R 1 -Q'}} -CO-
Are mentioned,
Wherein Q ′ and Q ″ independently represent O or NR ^a , R ^a is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R ¹ is one or more such as O or N Represents a linear, cyclic or branched alkylene group which may be interrupted by a heteroatom, wherein L ′ and L ″ each independently represents, for example, an alkylene group, a carbonyl group, a carbonamidoalkylene group and / or a carboxyalkylene group. A fluorinated organic divalent linking group is represented, and ^* indicates the position where the linking group is bonded to the group R _f in formula (IV).

The above fluorinated monomers R _f -L ⁵ -C (R) = CR ₂ and methods for their preparation are known and disclosed, for example, in US Pat. No. 2,803,615. Examples of such compounds include fluorochemical acrylates, methacrylates, vinyl ethers, and allylic compounds containing fluorinated sulfonamide groups, acrylates or methacrylates derived from fluorochemical telomer alcohols, acrylates derived from fluorochemical carboxylic acids Or, methacrylates, and the general class of perfluoroalkyl acrylates or methacrylates, as disclosed in EP 526 976.

  Perfluoropolyether acrylates or methacrylates are described in US Pat. No. 4,085,137.

ＣＦ₃（ＣＦ₂）₃ＣＨ₂ＣＨ₂ＯＣＯＣ（Ｒ’）＝ＣＨ₂

ＣＦ₃Ｏ（ＣＦ₂ＣＦ₂）_uＣＨ₂ＯＣＯＣ（Ｒ’）＝ＣＨ₂
Ｃ₃Ｆ₇Ｏ（ＣＦ（ＣＦ₃）ＣＦ₂Ｏ）_uＣＦ（ＣＦ₃）ＣＨ₂ＯＣＯＣ（Ｒ’）＝ＣＨ₂
Ｃ₃Ｆ₇Ｏ（ＣＦ（ＣＦ₃）ＣＦ₂Ｏ）_uＣＦ（ＣＦ₃）ＣＯＮＨＣＨ₂ＣＨ₂ＯＣＯＣ（Ｒ’）＝ＣＨ₂
ＣＦ₃ＣＦ₂ＣＦ₂ＣＦ₂Ｏ［ＣＦ（ＣＦ₃）ＣＦ₂Ｏ］_vＣＦ（ＣＦ₃）ＣＨ₂ＯＣＯＣ（Ｒ’）＝ＣＨ₂ （ｖは平均１．５）
が挙げられ、
式中、Ｒ’は水素またはメチルを表し、Ｒ’’はメチル、エチルまたはｎ−ブチルを表しおよびｕは約１〜２５である。 Particularly suitable examples of fluorinated monomers include
CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ OCOC (R ′) ═CH ₂
CF ₃ (CF ₂ ) ₃ CH ₂ OCOC (R ′) ═CH ₂

CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ OCOC (R ′) ═CH ₂

CF ₃ O (CF ₂ CF ₂ ) _u CH ₂ OCOC (R ′) ═CH _{2
C 3 F 7 O (CF (} CF 3) CF 2 O) u CF (CF 3) CH 2 OCOC (R ') = CH 2
_{C 3 F 7 O (CF (} CF 3) CF 2 O) u CF (CF 3) CONHCH 2 CH 2 OCOC (R ') = CH 2
CF ₃ CF ₂ CF ₂ CF ₂ O [CF (CF ₃ ) CF ₂ O] _v CF (CF ₃ ) CH ₂ OCOC (R ′) = CH ₂ (v is 1.5 on average)
Are mentioned,
Wherein R ′ represents hydrogen or methyl, R ″ represents methyl, ethyl or n-butyl and u is about 1-25.

  The fluorinated monomers according to formula (IV) or mixtures thereof typically have an amount of their associated units in the polymer of 10 to 97 mol%, preferably 25 to 97 mol%, more preferably 25 mol% to It is used in an amount of 85 mol%, most preferably 25 mol% to 75 mol%.

  The fluorinated monomer according to formula (IV) is generally copolymerized with one or more non-fluorinated monomers. In one embodiment, at least some of the non-fluorinated monomers are selected from chlorine-containing monomers such as vinyl chloride and vinylidene chloride. Such chlorine-containing monomer repeat units, if present, are preferably contained in the fluorinated polymer in an amount of 3 to 75 mole percent.

Additional non-fluorinated comonomers other than the chlorine-containing monomers referred to above include hydrocarbon group-containing monomers, such as monomers that can be represented by formula (V).
R _h -L ⁶ -E (II)
In the formula, R _h represents an aliphatic group having 4 to 30 carbon atoms, L ⁶ represents an organic divalent linking group, and E represents an ethylenically unsaturated group. The hydrocarbon group is preferably selected from the group consisting of linear, branched or cyclic alkyl groups, aralkyl groups, alkylaryl groups and aryl groups. Further non-fluorinated monomers include those in which the hydrocarbon group in formula (V) includes a substituent such as an oxyalkylene group; or a hydroxy group and / or a cure site.

Examples of non-fluorinated comonomers include hydrocarbon esters of α, β-ethylenically unsaturated carboxylic acids. Examples include n-butyl (meth) acrylate, isobutyl (meth) acrylate, octadecyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, cyclodecyl (meth) acrylate, isobornyl (meth) acrylate, phenyl ( (Meth) acrylate, benzyl (meth) acrylate, adamantyl (meth) acrylate, tolyl (meth) acrylate, 3,3-dimethylbutyl (meth) acrylate, (2,2-dimethyl-1-methyl) propyl (meth) acrylate, Cyclopentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, t-butyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate , Isooctyl (meth) acrylate, n- octyl (meth) acrylate, 4-ethyl - cyclohexyl (meth) acrylate, 2-ethoxyethyl methacrylate and tetrahydropyranyl acrylate. Further non-fluorinated comonomers include allyl esters such as allyl acetate and allyl heptanoate; alkyl vinyl ethers or alkyl allyl ethers such as cetyl vinyl ether, dodecyl vinyl ether, ethyl vinyl ether; acrylic acid, methacrylic acid, α-chloroacrylic acid, croton Acids, maleic acid, fumaric acid, itaconic acid and their anhydrides and their esters (vinyl, allyl, methyl, butyl, isobutyl, hexyl, heptyl, 2-ethylhexyl, cyclohexyl, lauryl, stearyl, isobornyl or alkoxyethyl acrylate and Unsaturated acids such as methacrylate); acrylonitrile, methacrylonitrile, 2-chloroacrylonitrile, 2-cyanoethyl acrylate Α-β unsaturated nitrile such as alkyl cyanoacrylate; allyl alcohol, allyl glycolic acid, acrylamide, methacrylamide, n-diisopropyl acrylamide, diacetone acrylamide, aminoalkyl (meth) acrylate (N, N-diethylaminoethyl methacrylate, N- α, β-unsaturated carboxylic acid derivatives such as t-butylaminoethyl methacrylate, etc .; the formula X ⁻ R ₃ N ⁺ —R ^a —OC (O) —CR ¹ ═CH ₂ , where X ⁻ is, for example, chlorine represents an anion such as the anion, R represents hydrogen or an alkyl group, and R may each be different even in the same, R ^a is R ¹ and represents an alkylene represents hydrogen or methyl) (meth ) Alkyl (meth) acrylates having ammonium groups such as acrylates; Styrene and derivatives thereof such as nyltoluene, α-methylstyrene, α-cyanomethylstyrene; ethylene, propylene, isobutene, 3-chloro-1-isobutene, butadiene, isoprene, chloro and dichlorobutadiene and 2,5-dimethyl-1, 5-hexadiene, ((meth) acrylate of polyethylene glycol, (meth) acrylate of block copolymer of ethylene oxide and propylene oxide, (meth) acrylate of amino- or diamino-terminated polyether and (meth) acrylate of methoxypolyethylene glycol) ) Hydrocarbon monomers containing (poly) oxyalkylene groups and (meth) acrylates such as (hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate) It includes lower olefin hydrocarbons which can contain halogen such as hydrocarbon monomers comprising a hydroxyl embraces radicals) hydroxyl group containing relations.

  In certain embodiments of the invention, the fluorinated polymer comprising units derived from the monomer according to formula (IV) further comprises units having one or more cure sites. These units will typically be derived from related comonomers having one or more cure sites. The term “cured site” refers to a functional group that can bind during reaction with the substrate to be treated. Examples of cured sites include acid groups such as carboxylic acid groups, hydroxy groups, amino groups and isocyanate groups or blocked isocyanate groups. Examples of comonomers from which cure site units can be derived include (meth) acrylic acid, maleic acid, maleic anhydride, allyl methacrylate, hydroxybutyl vinyl ether, N-hydroxymethyl (meth) acrylamide, N-methoxymethyl acrylamide, N- Butoxymethyl acrylamide, N-isobutoxymethyl acrylamide, glycidyl methacrylate and α, α dimethyl m. An example is isopropenyl benzyl isocyanate. Other examples are polymerizations obtainable by reaction of polymerizable mono-isocyanates with isocyanate blockers, or by reaction of di- or poly-isocyanates and hydroxy or amino-functionalized acrylates or methacrylates and isocyanate blockers. Include urethane. An isocyanate blocker is a compound that, upon reaction with an isocyanate group, is a group that is non-reactive at room temperature with a compound that normally reacts with isocyanate at room temperature, but generates a group that reacts with an isocyanate-reactive compound at high temperature. . In general, at elevated temperatures, blocking groups will be released from the blocked (poly) isocyanate compound, which will again produce isocyanate groups that can then react with isocyanate-reactive groups. Blockers and their mechanisms are described in “Blocked isocyanates III .: Part A, Mechanisms and Chemistry,” Douglas Wicks and Zeno W. Wicks Jr., Progress in Organic Coatings, 36 (1999), pp. 14-172.

  The blocked isocyanate can be aromatic, aliphatic, cyclic or acyclic, and is generally a blocked di- or triisocyanate or mixtures thereof, and the isocyanate can be reacted with isocyanate groups at least It can be obtained by reacting with a blocking agent having one functional group. Preferred blocked isocyanates are blocked polyisocyanates that can react with isocyanate-reactive groups through deblocking of the blocking agent at temperatures below 150 ° C., preferably at elevated temperatures. Preferred blocking agents include aryl alcohols such as phenol, lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, formaldoxime, acetoaldoxime, methyl ethyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime, 2- Examples include oximes such as butanone oxime or diethylglyoxime. Specific examples of comonomers having blocked isocyanate groups as cure sites include reaction products or diisocyanates of diisocyanate, 2-hydroxyethyl (meth) acrylate and 2-butanone oxime, mono (meth) acrylate of polyethylene glycol and 2- The reaction product of butanone oxime, and the reaction product of triisocyanate, 1 equivalent of 2-hydroxyethyl (meth) acrylate and 2 equivalents of 2-butanone oxime, and α, α-dimethyl m. The reaction product of isopropenyl benzyl isocyanate and 2-butanone oxime is mentioned.

In yet a further embodiment related to the present invention, the fluorochemical compound used in the composition is an alkylated fluorochemical oligomer disclosed in US Pat. No. 6,525,127. The alkylated fluorochemical oligomer disclosed in this US patent is:
(I) a fluorochemical oligomer moiety comprising an aliphatic backbone having a plurality of linked fluoroaliphatic groups (the fluoroaliphatic groups each having a fully fluorinated end group and each independently an aliphatic backbone carbon Connected to the atom via an organic linking group),
(Ii) an aliphatic moiety having at least 12 carbon atoms;
(Iii) a linking group that links the fluorochemical oligomer moiety and the aliphatic moiety.

  Compositions comprising a fluorinated compound and a carbodiimide or a mixture of carbodiimides can be prepared by blending an aqueous dispersion of carbodiimide or a carbodiimide mixture with a fluorinated compound. In order to improve the fixation of the composition of the present invention to the substrate, the dispersion includes certain additives, polymers, thermally cohesive products and catalysts capable of promoting interaction with the substrate. It may be advantageous. Among these are urea or melamine and formaldehyde aggregates or pre-aggregates (sometimes referred to herein as resins) and glyoxal resins. Certain suitable additives and their amounts can be selected by those skilled in the art.

  The amount of treatment composition applied to the substrate should generally be selected to provide a sufficiently high or desired water / oil repellency on the substrate surface, and the amount is usually based on 0.01% to 5% by weight, preferably 0.05% to 2% by weight based on the weight of the material and the weight of the water repellent composition (fluorinated compound and carbodiimide compound or carbodiimide compound mixture) The amount is present on the substrate. The amount sufficient to impart the desired water repellency (oil) properties can be determined empirically and can be increased as needed or desired.

  The carbodiimide compound or mixture of carbodiimide compounds is generally present in the treatment composition in an amount sufficient to improve the fluorine effect of the fluorinated compound. As used herein, “improving the fluorine effect” refers to an improved or equivalent water repellency when a portion of the fluorinated compound, preferably 10 to 50% by weight of the fluorinated compound, is replaced by carbodiimide. Oil) characteristics are obtained. Generally, the carbodiimide compound or mixture of carbodiimide compounds is in an amount of about 5 to about 500, preferably about 10 to about 200, and most preferably about 25 to about 100 parts by weight, based on 100 parts by weight of the fluorinated compound. Exists.

  The composition of the present invention can be applied using conventional application methods and can be used in particular as an aqueous dispersion. The dispersion generally contains an amount of the composition effective to provide water, water repellent (oil) properties to the treated substrate, and an amount of surfactant effective to stabilize the dispersion. Will. Water is preferably present in an amount of about 70 to about 20000 parts by weight based on 100 parts by weight of the composition of the present invention. The surfactant is preferably present in an amount of about 1 to about 25 parts by weight, preferably about 5 to about 10 parts by weight, based on 100 parts by weight of the composition of the present invention. Conventional cationic, nonionic, anionic, zwitterionic surfactants or mixtures thereof are preferred.

  In order to carry out the treatment of the substrate, the dispersion can be sprayed onto the substrate, or the substrate can be immersed in the dispersion and stirred until impregnated. The impregnated substrate can then be passed through a padder / roller to remove excess dispersion. The composition according to the present invention is for use in an application method wherein the substrate is contacted with the composition in a bath containing the composition and the substrate is guided to one or more rolls so that the composition is applied to the substrate. Particularly preferred. Typically, such rolls are configured to squeeze excess treatment composition from the substrate.

  Following application of the composition to the substrate, the substrate will generally be dried. The substrate can be dried at ambient conditions by exposing the substrate to air for a period of time. Good and effective water repellent (oil) properties can be achieved with the composition according to the invention even when dried at ambient conditions (generally 20-30 ° C.). Alternatively, the substrate can be exposed to heat following application of the composition to accelerate drying of the substrate and / or to cure the applied composition, if desired or necessary. When exposed to the heating temperature, the substrate can be introduced into an oven and the temperature of the heat treatment can be 100-200 ° C, typically 120-180 ° C.

  The amount of treatment composition applied to the substrate in accordance with the present invention is selected to provide a sufficiently high or desired water / oil repellency on the substrate surface, said amount usually being the weight of the substrate , In an amount such that 0.01% to 5% by weight, preferably 0.05% to 2% by weight, is present on the treated substrate, based on the amount of water repellent composition (fluorinated compound and carbodiimide). is there. The amount sufficient to impart the desired water repellency (oil) properties can be determined empirically and can be increased as needed or desired.

  The substrate to be treated by the water / oil repellency imparting composition of the present invention is not particularly limited, and examples thereof include knitted fabric, fiber, nonwoven fabric, leather, paper, carpet, plastic, wood, metal, glass, concrete and stone. Can be mentioned. Woven fabrics, fibers and non-woven fabrics are preferred.

  The invention is further illustrated with reference to the following examples, however, it is not intended that the invention be limited thereto.

Formulation and Treatment Method A treatment bath containing a specified amount of fluorinated compound and carbodiimide was formulated. Unless otherwise stated, treatments are padded at a concentration that provides a treatment composition of 0.3% or 0.6% solids (expressed on the basis of fabric weight and shown as SOFs (solids on fabric)). Applied to the test substrate. Drying and curing were performed at 160 ° C. for 1.5 minutes.

Test method water repellency (SR)
The water repellency of the treated substrate is a value indicating the dynamic water repellency (oil) property of the treated substrate with respect to the water hitting the treated substrate. Water repellency (oil) was measured and tested according to Test Method 22-1996 in the American Association of Textile Chemistry and Colorists (AATCC) Technical Manual published in 2001. Expressed in terms of the “water repellency” of the material. Water repellency was obtained by spraying 250 mL of water onto the substrate from a height of 15 cm. Wetting patterns were visually evaluated using a scale of 0-100. Here, 0 means completely wet and 100 means not wet at all.

Oil repellency (OR)
The oil repellency of the substrate was determined by the American Association of Textile Chemistry and Colorists (AATCC) standard test method no. 118-1983. This test was based on the durability of the treated substrate against penetration by different surface tension oils. Only treated substrate durability to Nujol (R) mineral oil (lowest permeability among test oils) got a rating of 1, whereas heptane (best penetration among test liquids) The treated substrate durability with respect to (a) was evaluated as 8. Other intermediate values were determined by using other pure oils or mixtures of oils as shown in the table below.

Bundesmann test The effect of impregnation of the rain on the treated substrate was measured using the Bundesman test method (DIN 53888). In this test, the treated substrate was subjected to simulated rain while rubbing the back of the substrate. The appearance of the exposed top surface was visually inspected after 1, 5 and 10 minutes and was rated from 1 (complete surface wetting) to 5 (no water left on the surface). Furthermore, in addition to the observation of the wetting pattern, the water absorption (% abs) was also measured. A well-treated sample gave low absorption results.

Water repellent test (WR)
The water repellency (WR) of the substrate was measured using a series of water-isopropyl alcohol test liquids and expressed in terms of the “WR” rating of the treated substrate. The WR rating corresponds to the most permeable test liquid that did not penetrate or wet the substrate surface after 15 seconds of exposure. Substrate soaked in or only resistant to 100% water (isopropyl alcohol 0%) (the least permeable test liquid) gave a rating of 0, while 100% isopropyl alcohol (0% water) A rating of 10 was given to the substrate resistant to (the most permeable test liquid). Another interim rating was calculated by dividing the percent isopropyl alcohol in the test liquid by 10. For example, a treated substrate that is resistant to a 70% / 30% isopropyl alcohol / water blend but not to an 80% / 20% blend would be given a rating of 7.

Laundry technique Using the technique defined below, a treated substrate sample, designated as 5HL IR (5 home laundry-ironing) in the following examples, was prepared.

A 230 g sample, which is a sheet of treated substrate, generally 400 cm ² to about 900 cm ² in a square, is placed in a washing machine in a ballast sample (8 oz of an edge-bent 8100 cm ² sheet, generally in the form of a square. 1.9 kg of cloth). A commercial detergent (“Sapton”, available from Henkel, Germany, 46 g) was added and the washing machine was filled to high water with warm water (40 ° C. ± 3 ° C.). The substrate and ballast charge were washed 5 times using a 12 minute normal wash cycle followed by 5 rinse cycles and dewatering. Samples were not dried between cycles. After drying, the sample was pressed using an iron set at a temperature for the substrate fibers.

The abbreviation Etoquad® C-12: cocobis (2-hydroxyethyl) methylammonium chloride (75% in H ₂ O) from Akzo-Nobel
iBMA: isobutyl methacrylate IPDI: isophorone diisocyanate GMS: glycerol monostearate ODA / HDA: 50/50 blend of octadecyl acrylate and hexadecane acrylate, available from Cognis as Photomer 4818F,
ODA: Octadecyl acrylate, available from Osaka.
4,4′-MDI: 4,4 ′ methylene diphenyl diisocyanate, available from BASF AG (BASF AG.) MIBK: methyl isobutyl ketone (4-methyl 2-pentanone)
MMA: methyl methacrylate ODI: octadecyl isocyanate ODMA: octadecyl or stearyl methacrylate VCL ₂ : vinylidene chloride CPPO: camphene phenylphosphine oxide catalyst Tergitol® TMN-6: trimethyl from Rohm & Haas Nonane polyoxyethylene (6EO) surfactant Tergitol® 15S30: C12-14 alkyl polyoxyethylene (30EO) surfactant from Rohm & Haas PCD: Polycarbodiimide Prizoline ( Prisorine) 3515: iso-stearyl alcohol, RBU obtained from Uniquema: roll deposition

PES / CO (2681.4): polyester / cotton 65/35, Utex Bell N. V. PAμ (7819.4) obtained from (Utexbel NV, Ronse, Belgium): polyamide microfiber, style no. 7819.4, PES (0030.1) obtained from Sofinal, Belgium: polyester, style no. 303.1, PESμ obtained from Radici, Italy, Italy: Polyester moss microfiber peach effect (filed), Sunline Surface Fabric co. PA: Apparel Polyamide taffeta (190 or 210 yarn fiber), available from Sunny Specific Mill

FC: fluorochemical acrylate having the following monomer composition C ₄ F ₉ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOC (CH ₃ ) = CH ₂ / VCL ² / ODMA (weight ratio: 60/20/20) And 3% Tergitol (R) based on 2% Etoquad (R) C-12 / 5.4% Tergitol (R) TMN-6 and fluorochemical acrylate solids ) 45% solids aqueous dispersion containing 15S30 emulsifier system.

Synthesis of carbodiimide extenders a. Synthesis of Reference Carbodiimide: Polycarbodiimide was prepared in the first step, shown as 4MDI / stearyl alcohol / isostearyl alcohol, and c-PCD. In a three-neck reaction flask equipped with a thermometer, Dean Stark condenser, mechanical stirrer, heating mantle and nitrogen inlet, 13.5 g (0.05 eq.) Stearyl alcohol, 13.5 g (0. 05 eq.) Prizoline 3515 and 167 g MIBK. 50 g of MIBK / H ₂ O azeotrope was evaporated through a Dean Stark condenser. After replacing the Dean Stark with a normal reflux condenser, the mixture was cooled to 65 ° C. and 50 g of MDI (0.4 eq.) Was added. The reaction mixture was heated at 75 ° C. for 3 hours. Then 5.0 g CPPO (20% solution in dichloromethane) was charged. The reaction mixture was heated at 90 ° C. for 16 hours. FTIR analysis showed complete conversion.

  In the second step, 80 g of the reaction mixture was emulsified. The PCD solution was added to an Etoquad® C-12 (2% solids), Tergitol 15S30 (3% solids) and Tergitol using a Branson 450 ultrasonic homogenizer. ) (R) TMN-6 (5.4% solids). The solvent was stripped on a Buchi evaporator using a water pump. A stable, emulsified dispersion was obtained.

b. 8MDI / 2 isostearyl alcohol _{/ (8ODA / HDA-HSCH 2} CHOHCH 2 OH) Synthesis of, in yet a first step shown as PCD-1, was prepared functionalized ODA / HDA oligomer. A 250 mL polymerization bottle was charged with 86.4 g ODA / HDA (267 meq.), 3.6 g 2-mercaptopropanediol (33 meq.), 60 g MIBK and 0.26 g Vazo 67. The mixture was degassed repeatedly using a water pump followed by vacuum break in a nitrogen atmosphere. The polymerization bottle was sealed and preheated in a Launder-o-meter at 75 ° C. for 20 hours. A clear, very slightly yellow, 60% solids non-viscous oligomer solution was obtained.

In the second step, a 500 mL three-necked reaction flask equipped with a thermometer, Dean Stark condenser, mechanical stirrer, heating mantle and nitrogen inlet was charged with 67.5 g of ODA / as prepared above. An HDA oligomer solution (50 meq.), 13.5 g isostearyl alcohol (50 meq.) And 153 g MIBK were charged. 50 g of MIBK / H ₂ O azeotrope was evaporated through a Dean Stark condenser. After replacing the Dean Stark with a normal reflux condenser, the mixture was cooled to 65 ° C. and 50 g of MDI (400 meq.) Was added. The reaction mixture was heated at 75 ° C. for 30 minutes.

  In the third step, a carbodiimidization reaction was performed. 5.0 g camphene phenylphosphine oxide catalyst (CPPO, 20% solution in dichloromethane) was added. The reaction mixture was heated at 95 ° C. overnight, producing a slightly cloudy, non-viscous solution. FTIR analysis showed complete conversion.

  The reaction mixture was emulsified as follows. 300 g of the polycarbodiimide solution as prepared above was heated to 65 ° C. and Etquad® C-12 (at 2% solids), Tergitol 15S30 (at 3% solids) and Tergitol (R) TMN-6 (5.4% solids) was added to a warm aqueous solution. 199 g of water was added. The mixture was emulsified at 220/20 bar (2 passes) with a two-step laboratory Manton-Gaulin. The solvent was stripped on a Buchi evaporator using a water pump. A stable, 21.9% solids emulsified dispersion was obtained.

c. Synthesis of 4MDI / isostearyl alcohol / (8iBMA-HSCH ₂ CH ₂ OH), and in the first step shown as PCD-2, iBMA oligomer was prepared. A 500 mL polymerization bottle was charged with 94.7 g iBMA (667 meq.), 6.5 g 2-mercaptoethanol (83.3 meq.), 67.4 g MIBK and 0.284 g V-59. The mixture was repeatedly degassed using a water pump followed by vacuum break in a nitrogen atmosphere. The polymerization bottle was sealed and preheated in a Launder-o-meter at 75 ° C. for 16 hours. A clear, colorless, 60% solids non-viscous oligomer solution was obtained.

In the second step, 60.7 g of the iBMA oligomer solution as prepared above was added to a three-necked reaction flask equipped with a thermometer, Dean Stark condenser, mechanical stirrer, heating mantle and nitrogen inlet. (30 meq.), 8.1 g isostearyl alcohol (30 meq.) And 138.4 g MIBK. 50 g of MIBK / H ₂ O azeotrope was evaporated through a Dean Stark condenser. After replacing the Dean Stark with a normal reflux condenser, the mixture was cooled to 65 ° C. and 30.3 g MDI (240 meq.) Was added. The reaction mixture was heated at 75 ° C. for 2 hours.

  In the third step, a carbodiimidization reaction was performed after the addition of 3.0 g camphene phenylphosphine oxide catalyst (CPPO, 20% solution in dichloromethane). The reaction mixture was heated at 95 ° C. for 16 hours, producing a slightly cloudy, non-viscous solution. FTIR analysis showed complete conversion.

  150 g of the reaction mixture was emulsified according to the method described for PCD-1.

  Polycarbodiimide PCD-3 to PCD-5 shown in Table 1 were prepared according to the same method.

d. 5MDI / 2 (4MMA-HSCH ₂ CH ₂ OH) / GMS) In the first step shown as PCD-6, in a 500 mL polymerization bottle, 80 g MMA (0.8 eq.), 15.6 g 2-mercaptoethanol (0.2 eq.), 63.7 g MIBK and 0.24 g V-59 were charged. The mixture was repeatedly degassed using a water pump followed by vacuum break in a nitrogen atmosphere. The polymerization bottle was sealed and preheated in a Launder-o-meter at 75 ° C. for 16 hours. A clear, colorless, 60% solids inviscid oligomer solution was obtained.

In the second step, a 3 neck reaction flask equipped with a thermometer, Dean Stark condenser, mechanical stirrer, heating mantle and nitrogen inlet was added to 47.8 g as prepared in the first step. Of MMA oligomer solution (0.06 eq.), 40.74 g glycerol monostearate (0.06 eq.) And 144.4 g MIBK. 50 g of MIBK / H ₂ O azeotrope was evaporated through a Dean Stark condenser. After replacing Dean Stark with a normal reflux condenser, the mixture was cooled to 65 ° C. and 37.5 g MDI (0.3 eq.) Was added. The reaction mixture was heated at 75 ° C. for 2 hours to produce a clear solution.

  In the third step, 3.75 g CPPO was charged. The reaction mixture was heated at 95 ° C. for 16 hours. FTIR analysis showed complete conversion.

  150 g of the reaction mixture was emulsified according to the method described for reference PCD-1.

  Carbodiimide PCD-7 to PCD-10 having the composition shown in Table 2 were prepared according to the same method.

e. 12MDI / isostearyl alcohol _{/ (8ODA / HDA-HSCH 2} CH 2 OH) / 2GMS synthesis, in yet a first step shown as PCD-11, ODA / HDA oligomer _{(8ODA / HDA-HSCH 2 CH} 2 OH) Was prepared as described for the synthesis of ODA / HDA oligomers (8 ODA / HDA-HSCH ₂ CHOHCH ₂ OH) using mercaptoethanol instead of mercaptopropanediol.

In the second step, a 36.7 reaction flask equipped with a thermometer, Dean Stark condenser, mechanical stirrer, heating mantle and nitrogen inlet was charged with 26.7 g of ODA / HDA oligomer (8 ODA / HDA- An HSCH ₂ CH ₂ OH) solution (10 meq.), 2.7 g of isostearyl alcohol (10 meq.), 7.16 g of GMS (40 meq) and 82.9 g of MIBK were charged. 50 g of MIBK / H ₂ O azeotrope was evaporated through a Dean Stark condenser. After replacing Dean Stark with a normal reflux condenser, the mixture was cooled to 65 ° C. and 30 g MDI (240 meq.) Was added. The reaction mixture was heated at 75 ° C. for 2 hours.

  In the third step, 3.0 g camphene phenylphosphine oxide catalyst (CPPO, 20% solution in dichloromethane) was charged. The reaction mixture was heated at 95 ° C. for 16 hours to produce a slightly cloudy, non-viscous solution. FTIR analysis showed complete conversion.

  150 g of the reaction mixture was emulsified according to the method described for PCD-1.

It was prepared according to the polycarbodiimide 12MDI / isostearyl alcohol _{/ (8ODA / HDA-HSCH 2} CH 2 OH) / 4GMS ( further indicated as PCD-12) the same way.

Examples 1-28 and Comparative Examples C-1 to C-4
In Examples 1-28, as shown in Table 3, a general treatment method was used with blends of fluorinated compound (FC) (0.18% SOF) and various carbodiimides (with 0.12% SOF). The substrate was processed. Comparative Examples C-1 to C-4 were formed in the same manner, but using only FC (0.3% SOF). The treated fabric was tested for oil and water repellency. The results are shown in Table 3.

Examples 29 to 44 and Comparative Examples C-5 to C-7
In Examples 29-44, the same experiment was repeated with blends of FC (0.18% solids) and various polycarbodiimides (at 0.12% solids) as shown in Table 4. Processing was performed by padding to obtain 0.18% SOFFC and 0.12% SOFPCD. Comparative Examples C-5 to C-7 were formed using only FC (0.3% SOF) and without adding polycarbodiimide. After drying and curing at 160 ° C. for 3 minutes, the oil and water repellency properties were measured. The results are shown in Table 4.

Examples 45 and 46 and Comparative Example C-8
Examples 45 and 46 were conducted to evaluate roll deposition (RBU) during application of a blend of fluorinated compound and polycarbodiimide having the composition shown in Table 5. Thus, a 5 l bath with tap water and 2 g / l 60% acetic acid is used to dilute a treatment bath by diluting a certain amount of product dispersion corresponding to 45 g solids (60% FC and 40% PCD). Got ready.

  The polyamide substrate was subjected to a Butterworth padder through a continuous loop through a bath containing a blend of fluorinated compound and PCD. Bathtub stability and RBU were observed during 1 hour operation (speed: 25 m / min; pressure 80 psi). To quantify the RBU, a visual rating of 1 (violent RBU) to 5 (no RBU) was given. Comparative Example C-8 was similarly formed, but with a bath containing 60% FC and 40% comparative polycarbodiimide c-PCD.

Claims (4)

Carbodiimide compound has the formula ^{Q 1 -X 1 -CONH- (A 1} - (N = C = N) q) m -A 2 -NHCOX 2 -Q 2
Wherein X ¹ and X ² each independently represent O, S or NH, and A ¹ and A ² each independently represent those obtained by removing isocyanate groups from organic di- or triisocyanate compounds. Wherein q is 1 or 2, m has a value of 1-20, and Q ¹ and Q ² are hydrocarbon groups, catenary or a group that may contain one or more catenary or non-catenary heteroatoms Partially or fully fluorinated hydrocarbon groups that may contain one or more non-catenary heteroatoms and functional groups corresponding to any of the following formulae

Wherein G ³ and G ⁴ each independently represent hydrogen or a terminal group selected from the group consisting of radical initiator residues, wherein the radical initiator is one or more ethylenically unsaturated acrylic monomers. Used for the preparation of functionalized oligomers prepared by free radical oligomerization, wherein the radical initiator is selected from the group consisting of azo compounds, hydroperoxides, peroxyesters, and diacyl peroxides; _h represents two or more repeating units derived from one or more ethylenically unsaturated acrylic monomers, wherein the ethylenically unsaturated acrylic monomer comprises octadecyl (meth) acrylate, hexadecyl (meth) acrylate, methyl Methacrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, Soboruniru (meth) acrylate, ethylhexyl methacrylate, containing urethane groups (meth) acrylate, and is selected from the group consisting of mixtures thereof, L ² is from the group consisting of linear branched or cyclic aliphatic group or an aromatic group Represents a selected organic divalent linking group having 1 to 30 carbon atoms, and Q ³ represents a hydrocarbon group that can contain one or more catenary or non-catenary heteroatoms, or a catenary or non-catenary heteroatom. A monovalent aliphatic, partially or fully fluorinated aliphatic group or moiety or fully fluorine that represents one or more partially or fully fluorinated hydrocarbon groups, including straight-chain branched or cycloaliphatic groups or aromatic groups A group having 1 to 50 carbon atoms, selected from the group consisting of a modified polyether group, wherein A ³ and A ⁴ are each independently organic Represents those residues obtained by removing isocyanate groups from di- or triisocyanate compounds, X ³ and X ⁴ each independently represent O, S or NH, and s has a value of 1-20. , And t are 1 or 2, and L ³ represents an organic trivalent linking group having 1 to 30 carbon atoms selected from the group consisting of linear branched or cyclic aliphatic groups or aromatic groups And L ⁴ represents a hydrocarbon group containing or not containing one or more catenary or non-catenary heteroatoms, or a partial or fully fluorinated hydrocarbon group that may contain one or more catenary or non-catenary heteroatoms, Here, one of Q ¹ and Q ² corresponds to the group of the formula (A), (B), (D) or (E)
Selected from)
Or a mixture of two or more carbodiimide compounds.   A composition comprising a fluorinated compound and the carbodiimide compound according to claim 1 or a mixture of two or more thereof. The fluorinated compound has the formula:
R _f −L ⁵ −C (R) = CR ₂
Wherein R _f represents a perfluorinated aliphatic group having 3 or 4 carbon atoms, or a perfluorinated polyether group, L ⁵ represents an organic divalent linking group, and R each independently represents H or Represents a lower alkyl group having 1 to 3 carbon atoms)
The composition according to claim 2, which is a polymer compound comprising one or more repeating units derived from the fluorinated monomer.   A processing method comprising the step of contacting a substrate with the composition according to claim 2.